Process for the coloration of cellulose textile materials with reactive dyestuffs



l I i United States Patent PROCESS FOR THE COLORATION 0F CELLULOSETEXTILE MATERIALS WITH REACTIVE DYE- STUFFS Gerald Booth and Frank Hall,Manchester, England, assignors to Imperial Chemical Industries Limited,London, England, a corporation of Great Britain No Drawing. Originalapplication May 11, 1959, Ser. No. 812,146. Divided and this applicationNov. 18, 1959, Ser. No. 858,299

Claims priority, application Great Britain May 19, 1958 12 Claims. (Cl.8--54.2)

This invention relates to new water-soluble dyestuffs valuable for thecolouration of textile materials, for example textile materialscontaining protein and synthetic protein materials and more especiallytextile materials comprising vegetable and regenerated cellulose fibres.

This application is a division of our copending application Serial No.812,146, filed May 11, 1959, now abandoned, and is entitled to thefiling date thereof.

We have found that certain novel water-soluble dyestuffs, namelyWater-soluble dyestuffs containing the groupings hereinafter defined,can be chemically reacted with cellulosic fibres under simpleconditions, which may readily be, carried out in commercially availablemachinery used for dyeing or textile printing processes, that is to say,by treatment of the cellulose with an aqueous solution of the dyestuffand an alkali.

According to the present invention there are provided new water-solubledyestuffs characterised in that they contain at least one group of theformula:

Formula II wherein Z stands for the linkage -O--, -S--, or -SO,,, andwherein X stands for halogen, preferably chlorine or bromine. There maybe obtained by the use of such dyestuffs under conditions hereinafterdefined, coloured cellulose derivatives of the probable formula:

A-Z-CH GHCHz-O[cel1ulose] wherein Z has the meaning given above and Astands for the radical of a water-soluble coloured compound.

The new water soluble dyestuffs may be of any dyestuff series and inparticular may be members of the azo, especially monoazo, series, theanthraquinone and, preferably the phthalocyanine series, particularlythose which contain a 3-chloro-2-hydroxypropoxy group. The dyestuffs maybe metal-free or may contain metals; for example copper, nickel, cobaltor chromium may be present in complex formation in members of the azo orphthalocyanine series.

A preferred class of the new dyestuffs are those represented by theformula:

wherein A represents a radical containing from 1 to 3 sulphonic acidgroups, the said radical being selected from the group consisting ofN-naphthylazo, N-naphthylazopyrazolonyl, N-anthraquinonylamino andN-copper phthalocyanine sulphamyl radicals. Above all are preferred thedyestuffs of the copper phthalocyanine series containing from 2 to 3sulphonic acid groups and from 2 to 1(3'-chloro-2-hydroxypropoxyphenyl)sulphamyl groups attached to the benzrings of the phthalocyanine nucleus.

The new dyestuffs may be obtained by methods in themselves known fromthe art or used in practice for the synthesis of water-soluble dyestuffsby reaction of dyestufi intermediates at least one of which alreadycontains a group of the formula:

wherein X and Z have the above meanings, and at leas one of the saidintermediates containing a water-solubilising group.

In the azo series, for example aromatic amines contain ing groups ofFormulas I and II may be used as diazr components in the conventionalcoupling reaction. Suit able diazo components include, for example:

4-( 3-chloro-2-hydroxypropoxy) aniline, 4- 3 '-bromo 2'-hydroxypropoxy)aniline, 4 (3'chloro-2'-hydroxypro pylmercapto) aniline, 4(3'-chloro-2-hydroxypropylsul phonyl) aniline, 3aminophenyl-(3'-chloro-2-hydroxy) propylsulphone,2-(3'-chloro-2-hydroxypropoxy)aniline 5-sulphonic acid,2-(3'-chl0ro-2-hydroxypropoxy)anilint and3-(3'-chloro-2-hydroxypropoxy)aniline.

Similarly, coupling components containing grouping: of Formula I or ofFormula II may be used. These include, for example:

7-(2':3'-epoxypropoxy) 2 naphthol, 7-(3'-chloro-2" hydroxypropoxy) 2naphtho-l, 1 [4' (3"-chloro-2" hydroxypropoxy)phenyl] 3 methyl 5pyrazolone 2 naphthol 6 sulphon[4-(3"chloro-4"-hydroxypro poxy)anilide]and 6 (2'23' epoxypropylmcrcapto) 2 naphthol.

For the synthesis of azo dyestuffs in accordance witl the invention fromdiazo'and/or coupling component: containing the groups of Formula I orII above, the diazc and coupling components are so chosen that theresultan dyestufi contains at least one water-solubilising grouping Theabove amines'listed as diazo components can alst be used asintermediates for the synthesis of dyestuffs i1 series other than theazo series, for example, by reacting the amine with a dyestuffcontaining sulphonchloridt groups, for example, the phthalocyanines ofUnited King dom specification No. 515,637 or aminoor substituteamino-anthraquinones containing 2 or more sulphonchlo ride groups.

The proportion of amine used may be varied to obtaii differentproportions of sulphonamide groups and sul phonic acid groups, but, aswill be apparent, it is essen tial that at least one molecularproportion of the amint is used for each molecular proportion of thedyestui containing sulphonchloride groups. When the dyestuf containingsulphonchloride groups also contains sul phonic acid or otherwater-solubilising groups, an exces: of amine may be used over theamount necessary to reac completely with the sulphonchloride groupspresent 'When the dyestufr" containing su'lphonchloride group.

does not contain any Water-solubilising group, the pro portion of amineadded should be insuificient to caus complete conversion of all thesulphonchloride groups t( sulphonamide groups. Any sulphonchloridegroup. which do not react with the amine may be hydrolyse by earring outthe process in aqueous medium or b after-treating the dyestuffcontaining both sulphonchlo ride and sulphonamide groups in a weaklyalkaline aque ous solution; aqueous pyridine at a temperature of abou 25C. is particularly suitable for this hydrolysis step I the hydrochloricacid liberated during the reaction may )e neutralised by adding anacid-binding agent, for example, by adding a salt of a weak acid such assodium icarbonate, sodium carbonate or sodium acetate.

The above amines may also be reacted with other dyeitlllf intermediatescontaining reactive halogen atoms, for :xample,1-amino-4-bromoanthraquinone 2 sulphonic Mild to give blue dyestuffs,and o-chloronitrobenzene and ts sulphonic acid and similar compounds togive greenish ICllOW dyestuffs of the o-nitro-diarylamine series.

The new dyestuffs may also be obtained by treating a vater-solublecoloured compound containing at least one group of the formula:

vherein Z has the meaning given above and M stands for i hydrogen atomor an alkali metal such as sodium or Jotassium, with a 2:3-epoxypropylhalide, preferably :pichlorhydrin or epibromhydrin or with an alkali and7. 1:3-dihalogeno-2-propanol such as glycerol dichlorhylrin. Suitablecoloured compounds for use in this procss include, for example,3-carboxy-4-hydroxyazoben- :ene-4-sulphonic acid,3-carboxy-4-mercaptoazobenzenet-sulphonic acidl-amino-4(4-hydroxyanilino)anthra- 1uinone-2z5-disulphonic acid, andsulphonated copper phthalocyanines containing (4-hydroxy-3-sulphophenyl)sulphamyl, (3-hydroxy-4-carboxyphenyl) sulphamyl, (2-rydroxyethyl)sulphamyl, mercapto or mercaptomethyl {CH .SH) groups.

The new dyestuffs may be used for the colouration, by dyeing orprinting, of a wide variety of textile materials. Nitrogenous materialssuch as natural proteins, for example, wool, silk and leather, orsynthetics such as nylon or polyacrylonitrile may be dyed, for examplein hot acid, neutral or weakly alkaline aqueous solutions of thedyestuff.

The new water-soluble dyestuffs may be used for the colouration ofvegetable and regenerated cellulose fibres such as cotton, linen andviscoserayon, the treatment being carried out in conjunction with atreatment at elevated temperature with an alkali. When so applied thenew dyestuffs are believed to react chemically with the fibre, thisbelief being based on the resistance of the colouration to severewashing treatments and also to solvent extraction treatments. Thiscolouration process forms a further feature of the invention. I

'The above process may readily be adapted so that it may be carried outin the commercially-available machinery used for dyeing or textileprinting processes and for continuous or non-continuous variations ofsuch processes.

Thus the cellulose material may be impregnated with an alkali and withthe dyestulf and then subjected to a heating or steaming step in, forexample, a hot flue dryer, a molten metal bath, an oven or a stenter.

The impregnation may be carried out, for example, by padding thematerial in an aqueous solution containing both dyestulf and alkali or,in either order, through aqueous solutions containing separately thedyestulf and the alkali.

Preferably the material is padded in an aqueous solution of the dyestutland dried by any convenient means and the dried material is paddedthrough an aqueous solution of alkali and then steamed or heated forexample at between 100 and 130 .C.

The solution of dyestufl may contain adjuvants com monly-used in dyeing,for example urea, Wetting agents such as the condensation products offatty alcohols or alkylated phenols with ethylene oxide, sulphonatedoils, methylene dinaphthalene sulphonic acid oroleyl sodium sulphate andmigration inhibitors such as Glaubers salt, common salt, or sodiumalginate. t

The solution of alkali, particularly when used in the preferred mannerdescribed above, may contain alkaline and neutral electrolytes such assodium chloride, sodium sulphate and potassium chloride. Preferably,there is used a solution containing at least 0.5% by weight, andpreferably between 1% and 3% by weight of a caustic alkali such ascaustic soda or caustic potash, since the subsequent fixation of thedyestuif may then be achieved by a relatively short steaming step ofbetween 1 and 5 minutes, thus rendering the process particularlysuitable for continuous dyeing. Solutions containing a higherconcentration of alkali, for example up to 25 to 30% of alkali, may alsobe used.

When the alkali is added to the solution of dyestuff, there can be useda non-caustic alkali, to lessen premature hydrolysis of the reactivegroups. Preferably an alkali capable of giving a pH of at least 10 inaqueous solution is used, although there may also be used certain milderalkalis, for example alkali metal bicarbonates, which are converted toan alkali capable of giving a pH of at least 10 at the elevatedtemperature necessary to cause reaction of the cellulose with thedyestulf.

The treatment of the cellulose textile material with the dyestulf andthe alkali may also be carried out by textile printing methods, forexample by locally treating the textile :material with a printing pastecontaining the dyestuff and an alkali, and thereafter subjecting theprinted material to an elevated temperature, for example by a heating ora steaming step. Alternatively, the alkali may be applied in a separatestep, before or after printing the material with a printing pastecontaining the dyestuff.

The printing pastes used may contain the adjuvants commonly-used in theformation of textile printing pastes, for example, urea, wetting agentsas exemplified above, mild oxidising agents such as sodiumm-nitrobenzene sulphonate, and thickeningagents. As thickening agents,there may be used, for example, starch, British gum, gum tragacanth, oralkyl ethers of cellulose, but preferably there are used thickeningagents free from primary alcoholic hydroxyl groups, for example theemulsion thickeners described in United Kingdom specification No.524,803, or preferably alginates, especially sodium alginatc.

Since these preferred thickening agents are adversely affected bycaustic alkalis, it is preferred to use milder alkalis such as sodiumcarbonate, trisodium phosphate or sodium metasilicate when the alkali isadded to the printing paste. As in the dyeing recipes, an alkali capableof giving a pH of at least 10.0 in aqueous solution is necessary,although milder alkalis such as alkali metal bicarbonates which areconverted during the heating or steaming step to an alkali as definedabove, may be used.

It will be appreciated that any dyestuff which has been absorbed by thecellulose material but which has .not reacted with it, will behave as aso-called direct dyestuff and will be removable from the colouredcellulose by subsequent Washing treatments at a rate which depends uponits afiinity for cellulose. It is therefore a preferred feature of thepresent process to use dyestuffs having poor afiinity for cellulose whendyed in the absence of alkali, and to subject the coloured cellulose toa scouring treatment, for example by boiling in a dilute aqueoussolution of soap or detergent for at least 1 minute and preferably atleast 5 minutes, to remove unreacted dyestutf before finally drying thematerial.

When the dyestulf used in the colouration process contains suitablegroupings, for example diazotisable amino groups, aromatic hydroxyl orketo-enol groups or metallisable systems, the coloured cellulose may besubjected to further treatments e.g. with nitrous acid and then acoupling component; or with a diazotised amine; or with an agentyielding metal, to modify the shade or properties of the colouredcellulose.

The new coluration process may be applied to a wide variety of cellulosematerials, for example textile materials such as loose fibre of cottonand linen, viscose rayon filament and staple fibre, to fabrics Wovenentirely or partly from such fibres.

The resultant colourations are very fast to washing treatments, andaccording to the dyestuif residue attached thereto may be fast to light,to bleaching treatments, to treatments with acid and alkali, or to burntgas fumes. They are thus suitable for the manufacture of textilematerials with a high degree of washing fastness for example highquality shirtings and sheetings, and also for furnishing materials.

The invention is illustrated but not limited by the following examplesin which parts and percentages are by weight:

Example 1 4 parts of 4-(3-chloro-2'-hydnoxypropoxy)aniline, obtained asdescribed below, are dissolved in 60 parts of water and 4 parts ofaqueous hydrochloric acid of specific gravity 1.16 at 5 C. A solution of1.4 pants of sodium nitrite in pants of water is added during 10minutes. The mixture is stirred for 5 minutes and ex cess nitrous acidis removed by adding sulphamic acid. The diazo compound so obtained isadded to a suspension, cooled to 5 C., of 4.78 parts of2-amino8-hydroxynaphthalene-6-sulphonic acid in 60 parts of water andthe mixture is stirred for 20 hours at 5 C. 5 parts of sodiumbicarbonate are added and then sodium chloride is added at the rate of150 grams for each litre of mixture. The precipitated dyestulf isfiltered olf and dried. It is obtained in the form of a brown powderwhich dissolves readily in water to give a brown solution. Theorganically combined chlorine content of the product corresponds to 1atom of chlorine per azo link. The product colours cellulose textilematerials in brown shades very fast to Washing when applied inconjunction with an alkali, A number of-suitable recipes are given belowin Examples 3 to 6. p

'Ihe 4-(3'-chloro-2-hydroxypropoxy)aniline used in the above example maybe obtained as follows:

46 parts of 4-(3-chlo1 o-2-hydroxypropoxy)nitroben- ,zene obtainedaccording to the method described by Stephenson in the Journal of theChemical Society, 1954, at p. 1571, are dissolved in 370 par-ts of ethylalcohol and 10 pants of finely divided nickel are then added.

The mixture is then heated at from 40 to 50 C. for 6 hours in anautoclave with hydrogen at 100 atmospheres pressure, and cooled. Thesuspended nickel is removed by filtration and the resulting alcoholicsolution is evaporated to dryness. The residual oil consists of 39 partsof crude 4-(3-chloro#2'-hydroxypropoxy) aniline which can be purified byrecrystallization of its halfsulphate.

Example 23 parts of copper phthalocyanine are heated in 240 parts ofchloros-ulphonic acid at 138 C. for 4 hours, then the solution is cooledand drowned into ice and water. The precipitate, which consistssubstantially of copper phthalocyanine-tetra-(3)-sulphonchloride,' isfiltered off, suspended in 400 parts of water cooled to below 5 C. andthepH of the mixture isbrought to 7 by adding sodium carbonate.

Asol-ution of 16.1 parts of 4-(3'-chloro-2'- hydroxypropoxy)aniline in 50 pants of water and 8.1 parts of aqueous hydrochloric acid of specificgravity 1.16 is then added followed by the addition of 34 parts ofsodium.

greenish blue shades very fast to washing when applied in conjunctionwith an alkali by the recipes, or simple varations of the recipes,described in Examples 3 to 6.

Example 3 100 parts of cotton fabric are padded in a 2% aqueous solutionof the dyestulf of Example 1 containing 0.2% of a highly sulphonated oiland 2% of sodium sulphate, and squeezed until the weight of the fabricis 200 parts. The fabric is dried, padded in an 'aqeuous solutioncontaining 2% of caustic soda and 30% of sodium chloride and againsqueezed until its weight is 200 parts.

The fabric is then steamed for 1 minute at 100 C., then rinsed in water,boiled in'a dilute soap solution for five minutes, rinsed again in waterand dried.

The fabric is coloured a brown shade, very fast to washing.

Example 4 A print paste is prepared having the following composition:

Par-ts Dyestuif of Example 2 3.0 Urea 5.0 Water 55.5 Sodium alginate (5%aqueous solution) 35.0 Sodium bicarbonate 1.5

100 parts of viscose rayon yarn are added to a solution at 50 C.containing 1 part of the dyestulf used in Example 1 in 3,000 pants ofwater and parts of sodium chloride are then added. The solution is thenheated to 90 C. and treat-ment'continued at this temperature for 30minutes. A solution of 5 parts of caustic soda flake in Water is thenadded. After a further 60 minutes the viscose rayon is renroved, rinsedin water and finally soaped for 15 minutes in a boiling solutioncontaining 9 pants of an alkyl phenol-ethylene oxide condensate in 3,000parts of water and it is then rinsed in water and dried. The viscoserayon is dyed a brown shade.

A similar result is obtained trisodium phosphate is used in place of thecaustic soda.

Example 6 fast to washing.

Example 7 By carrying out the. procedure of Example 1 but addingsufiicient alkali to give a pH of about 9, a brownish-rm dyestuif isobtained. a

Example 8 4. parts of 4-(3'-chloro-2'-hydroxypropoxy) aniline artdiazotised as described in Example 1 and added to a solution of 7.3parts of 1 acetylamine-S-hydroxynaphtha lene-3z6-disulphonic acid and3.2 parts of sodium bicar bonate in 50 parts of water. The mixture isstirred a '2' 20 C. and at a pH of 8.8 for 1 hour, then sodium chlorideis added to precipitate the dyestuff which is filtered off and dried.The red powder so obtained contains 1 atom of organically bound chlorineper azo group. It dyes cellulose by the methods of Examples 3 to 6 inredviolet shades of good fastness to washing.

Example 9 16 parts of 4-(3-chloro-2-hydroxypropoxy)aniline, halfsulphate are dissolved in 60 parts of water and 16 parts of 36% aqueoushydrochloric acid, and diazotised at below 10 C. with a solution of 5.6parts of sodium nitrite in 80 parts of water, added over 10 minutes.After 5 minutes excess nitrous acid is removed by a small addition ofsulphamic acid. The diazo compound so obtained is added during 30minutes to a solution, cooled to C., of 19.2 parts of2-amino-5-hydroxynaphthalene-7- sulphonic acid and 13 parts of sodiumbicarbonate in 200 parts of water. The mixture is adjusted to pH 7 to 8by addition of 4 parts of sodium bicarbonate and stirred allowing thetemperature to rise to C. After 2 to 3 hours, the pH being in the range9 to 10, sodium chloride is added and the suspension of slightly tarryprecipitated dyestufi is stirred and cooled, to harden.. The dyestuif isfiltered off, washed on the filter with 10% brine and dried at 40 C.

The reddish-brown powder so obtained contains 1 atom of organicallybound chlorine per azo group. It dyes cellulose by the methods ofExamples 3 to 6 in dull red shades fast to washing.

By replacing the 19.2 parts of 2-amino-5-hydroxynaphthalene-7-sulphonicacid with 22.5 parts of Z-acetylamine- 5-hydroxynaphthalene-7-sulphonicacid, or with 27.5 parts of 2-benzoylamino-5-hydroxynaphthalene 7sulphonic acid, a dyestuff is obtained containing 1 atom of organicallycombined chlorine per azo group. Each dyes cellulose by the methods ofExamples 3 to 6 in red shades fast to washing. I I

Example 10 8 parts of 4-(3'-chloro-2'-hydroxypropoxyaniline) halfsulphate are diazotised as described in Example 9. The diazo compound soobtained is added to a solution, cooled to 5 C., of 10.1 parts of theurea of Z-amino-S-hydroxynaphthalene-7-sulphonic acid in 200 parts ofwater and 6.4 parts of sodium bicarbonate. The mixture is stirred for 18hours allowing the temperature to rise to 20 C., then sodium chloride isadded to coagulate the gelatinous dyestufr' suspension. The dyestuff soobtained is filtered off and dried at 40 C.

It is obtained as a reddish powder, containing 1 atom of organicallybound chlorine per azo group. It dyes cellulose by the methods ofExamples 3 to 6 in strong red shades fast to washing. 1

Example 11 4 parts of 2-(3-chloro-2-hydroxypropoxy) aniline arediazotised in the manner described in Example 1. Excess nitrous acid inthe diazo solution is removed with sulphamic acid. The diazo solution isadded to a suspension, cooled to 5 C., of 4.78 parts of2-amino-8-hydroxynaphthalene-6-sulphonic acid in 50 parts of water, then10 parts of sodium acetate crystals are added and the mixture is stirredfor 20 hours at 5 C. Sodium chloride is then added and the precipitateddyestuff is filtered off and dried.

It dyes cellulose by the methods of Examples 3 to 6 in brown-red shadesof good fastness to washing.

:The 2-(3'-chloro-2-hydroxypropoxy) aniline used in the above examplemay be obtained and purified in analogous manner to the method describedfor its para-isomer in Example 1. The sulphate melts at 175 to 176 C.

Example 12 By coupling diazotised 2-(3-chloro-2'-hydroxypropoxy) anilinewith l-acetylamino-8-hydroxynaphthalene-3:6-disulphonic acid in similarmanner to the method described inExample 8, a dyestuff is obtained whichdyes cellulose by the methods of Examples 3 to 6 in red-violet shadesfast to washing.

Example 13 If the 4-(3'-chloro-2-hydroxypropoxy)aniline used in Example8 is replaced by 3-(3-chloro-2-hydroxypropoxy)aniline, a dyestufi isobtained giving a rubine shade fast to washing when applied to celluloseby the methods of Examples 3 to 6.

The 3-(3'-chloro-Z-hydroxypropoxy)aniline used in the above example maybe obtained and purified in analogous manner to the method described forits para-isomer in Example 1. The sulphate melts at to C.

Example 14 If the 2-(3-chloro-2-hydroxypropoxy)aniline used in Example11 is replaced by 3-(3'-chloro-2-hydroxypropoxy)aniline a dyestufl isobtained giving brown-red shades fast to washing when applied tocellulose by the methods of Examples 3 to 6.

Example 1 5 If the 2-(3-chloro-2-hydroxypropoxy)aniline used in Example8 is replaced by 5.04 parts of 1-chloro-3-(maminobenzyloxy)-2-propanolhydrochloride, a dyestuif is obtained which dyes cellulose by themethods of Examples 3 to 6 in dull red shades of good fastness towashmg.

Example 17 By replacing the 4-(3-chloro-2'-hydroxypropoxy)aniline usedin Example 8 by 5.1 parts of 4-(3'-chloro-2-hydroxypropylmercapto)aniline hydrochloride, a dyestutf is obtainedwhich dyes cellulose by the methods of Examples 3 to 6 in violet shadesof good fastness to washing.

The 4-(3-chloro-2f-hydroxypropylrnercapto)aniline hydrochloride used inthe above example may be obtained as follows:

87 parts of p-nitrothiophenol, 1 part of piperidine and 168 parts ofepichlorhydrin are stirred in 600 parts of dry toluene at 95 C. for 45minutes. The toluene is removed by distillation at 15 mm. pressure andthe product is dissolved in 175 parts of benzene and is twiceprecipitated by addition of petroleum. The oil is then dissolved in 350parts of benzene and the solution is Washed with an equal volume of 36%aqueous hydrochloric acid, and then with water until free from acid. Thesolution 15 then evaporated to give a yellow solid melting at 41 to 43C.

65 parts of the product so obtained are dissolved in 325 parts ofmethanol and hydrogenated at 50 C., atmospheres pressure in the presenceof Raney nickel catalyst. The catalyst is filtered off, the methanol isremoved by distillation and residual oil is dissolved in chloroform andtreated with dry hydrochloric acid. A tar precipitates and this istriturated with ethyl acetate until it solidifies.

Example 18 If the 4-(3'-cl1loro-2-hydroxypropoxy)aniline used in Example8 is replaced by 5 parts of 4-(3-chloro-2-hydroxypropysulphonyl)aniline,a dyestufi is obtained which yields dull red shades of good fastness towashing when applied to cellulose by the methods described in Examples 3to 6.

The 4-(3'-chloro 2' hydroxypropylsulphonyl)aniline used in this examplemay be obtained by oxidising 3-(4'- nitrophenylthio)-2-hydroxypropylchloride with hydrogen peroxide in acetic acid and catalyticallyreducing the product so obtained in the presence of Raney nickel. Itmelts at 126 to 128 C.

Example 19 If the 2-(3' chloro-2'-hydroxypropoxy)aniline used in Example11 is replaced by 5 parts of4-(3-chloro2.-hydroxypropylsulphonyl)aniline, a dyestufl? is obtainedwhich dyes cellulose by the methods of Examples 3 to 6 to give redshades of good tastness to washing. 1

Example 20 6.1 parts of Z-aminonaphthalene-l:5-disulphonic acid isstirred with 50 parts of water and 4 pants of aqueous hydrochloric acidof specific gravity 1.16 and diazotised at 5 C. by addition of 1.4 partsof sodium nitrite. After ten minutes the excess nitrous acid is removedwith sulphamic acid and the diazo compound is added to a solution at 5C. of 5.7 pants of 1-[4-(3-ch1oro-2-hydroxypropoxy)phenyl] 3 methyl- 5pyrazolone in 50 parts of ethylene glycol monomethyl ether, 200 parts ofwater, 0.8 part of sodium hydroxide and 8 parts of sodium acetatecrystals. The mixture is stirred for 1 hour, then sodium chloride isadded and the dyestulf which precipitates is filtered ofi, washed with5% brine and dried.

The yellow powder so obtained contains one atom of organically boundchlorine per azo group. It dyes cellulose by'the methods of Examples 3to 6 in yellow .shades of good fastness to washing.

Examples 21 to 28 If in the processof Example 2, the 16.1 parts of4-(3'- chloro-Zf-hydroXypropoxy)aniline are replaced by:

(2 1) 10.1 parts of 4-(3' chloro-Z' hydroxypropoxy)- aniline, (22) 17.4parts of 4-(3'-chloro-2=hydroxypropylmercapto) aniline, I

(23) 10.1 parts of 2-(3'-chloro-2'ahydroxypropoxy)- aniline,

(24) .121 parts of 2-(3'-ch1oro-2'-hydroxypropoxy)- aniline,

(25) 10.1 parts of 3-(3'-chloro-2' hydroxypropoxy)- aniline,

(26) 12.1 parts of 3-(3'-chloro-2'=hydrox'ypropoxy)- aniline,

(27) 1 1.8 parts of 1-chloro-3-(m-arninobenzyloxy)- Z-propanol, or

(28) 12.9 parts of -1 chloro-3-(m-aminobenzyloxy)- 2-lpropanol dyestuffsare obtained which have, in general, similar properties to those of thedyestuif of Example 2, in that they give greenish-blue shades of goodfastness to washing when applied to cellulose bythe methods of Examples3 to 6.

Examples 29 to 36 (30) 10.1 parts of 4-(3'-chloro-2'-hydroxypropoxy)-aniline,

(31) 10.1 parts of 2-(3'-chloro-2-hydroxypropoxy)- aniline,

(32) 12.1 parts of 2-(3'-chloro-2-hydroxypropoxy)- aniline,

(33) 10.1 parts of 3-(3'-chloro-2'-hydroxypropoxy)- aniline,

(34) 12.1 parts of 3-(3-chloro-2-hydroxypropoxy)- aniline,

(35) 11.8 parts of 1=chloro-3-(m-aminobenzyloxy)-2- propanol, or

(36) 12.9 parts of 1-ch1oro3-(m-aminobenzyloxy) -2- propano'l.

Example 37 46 parts of copper phthalocyanine are chlorosulphonated usingthe conditions described in Example 2 and the solution is drowned intoice-water, filtered oil and washed well 'with water. The paste soobtained is added during 1 hour to a stirred mixture of 291 parts ofsodium bisulphite and 73.6 parts of sodium hydroxide in 1000 parts ofwater, keeping the pH at from 7.0 to 7.5 by adding 10% aqueous sodiumcarbonate solution as necessary. 18.5 parts of sodium} bicarbonate areadded and the mixture is stirred at 20 .C. for 18 hours. Sufficientaqueous caustic soda solution is then added to give a pH of 10.5 and themixture is stirred for 1 hour.

7 The mixture is then acidified to methyl orange and the ;of Water isadded.

precipitate is filtered oil and dried.

The product so obtained on titration with nitrous acid is found to haveone sulphinic acid and 3 sulphonic acid groups in the molecule.

25.6 parts of the product so obtained, containing 17.6 (0.02 mole.) ofthe pure compound are dissolved in 220 parts of water by adding 4%aqueous caustic soda until the pH of the mixture is 6.4. The solution isfiltered and a solution of 4.55 parts of disodium hydrogen phosphate and7.5 parts of sodium dihydrogen phosphate in 40 parts 11.4parts ofepichlorhydrin are added and the solution is stirred at 55 to 60 C. for

bonus. The mixture is made acid to methyl orange and group) in themolecule. It dyes cellulose by the methods described in Examples 3 to 6in greenishblue shades of good fastness to washing.

Example 38 A solution of 13.95 parts of sodium,1-an1ino-4-bromoa-nthraquinone-2-sulp'honate in 300 parts of water isadded to a stirred mixture of 0.25 part of CuSO 5H O, 0.25 part of Ou Cland 22.38 parts NaHCO in 300 parts water. Then 18.0 parts ofp-(3-rchloro-2'-hy droxy)propoxy aniline sulphate are added during 10minutes. The mixture is warmed to 65 .C. and stirred for 45 minutes,filtered hot, cooledand 65 parts of salt are added to the coldfiltrates. An oil is produced which solidifies on standing for severalhours. The solid so obtained is filtered off and purified by dissolvingin 750 parts of water at 50 C., filtering and saltin g the filtrateswith 75 parts of salt. This operation is repeated three times and it isthen dried.

The product so obtained dyes cellulose in blue shades of good fastnessto washing when applied by the methods of Examples 3 to 6.

What we claim is:

. 1. Process for the coloration of cellulose textile materials with awater-soluble dyestufi characterized by one of the formulae wherein Zstands for a linkage selected from the group consisting of --O, S and"-SO2; X stands for a halogen atom selected from the group consisting ofbromine and chlorine; and A represents the radical of a Water-solublecolored compound of a dyestuff series selected from the class consistingof azo, anthraquinone and phthalocyanine series; which process comprisestreating the said materials with said dyes'tuif in aqueous medium inconjunction with a treatment of said materials with an alkali at anelevated temperature.

2. Process according to claim 1 wherein said Watersoluble dyestuff is ofthe formula wherein A represents a radical containing from 1 to 3sulphonic acid groups, the said radical being selected from the groupconsisting of N-naphthylazo, N-naphthylazopyraz olonyl,N-anth-raquinoylarnino and N-copper phthalocyanine sulpha'myl radicals.

3. Process according to claim 1 wherein said watersoluble dyestuft is ofthe copper phthalocyanine series containing from 2 to 3 sulfonic acidgroups and from 2 to 1 (3'-chloro-2'-hydroxypropoxypropyl) sulpharnylgroups attached to the benzine rings of the phthalocyanine nucleus.

4. Process according to claim 1 wherein the cellulose material is paddedthrough an aqueous solution of the dyestuff and then through an aqueoussolution of the alkali, and then the impregnated material is subjectedto elevated temperature.

5. Process according to claim 1 wherein the cellulose material is paddedthrough an aqueous solution of the alkali and then through an aqueoussolution of the dyestuif and then the impregnated material is subjectedto elevated temperature.

6. Process according to -claim. 1 wherein the cellulose 12 through anaqueous solution of alkali and then treated at between 100 C. and 130 C.

8. Process for the localised colouration of cellulose textile materialaccording to claim 1 which comprises applying locally to the materiala'printing paste containing the dyestutf and an alkali, and thereaftersubjecting the printed material to an elevated temperature.

9. Process as claimed in claim 1 wherein the alkali used is capable ofgiving a pH of at least in aqueous solumaterial is impregnated with analkali and with the dyetion.

10. Process as claimed in claim 1 wherein the alkali used is itselfincapable of giving a pH of 10 in aqueous solution, but is converted toan alkali capable of giving a pH of at least 10 during the treatment atan elevated temperature.

11. Process as claimed in claim 1 wherein the dyestulf used has a poorafiinity for cellulose when dyed in the absence of alkali, and thecoloured textile material is subjected to a scouring treatment.

12. Coloured cellulose derivatives of the formula:

wherein Z is selected from the class consisting of O, S and SO and Astands for the radical of a water-soluble coloured compound selectedfrom the class consisting of water-soluble azo, anthraquinone, andpht-halocyanine dyestuffs.

References Cited in the file of this patent UNITED STATES PATENTS1,935,624 Ellis et al Nov. 21, 1933 1,935,657 Mosby et a1. Nov. 21, 19331,986,801 Ellis Jan. 8, 1935 2,131,712 Schoeller et a1. -1 Sept. 27,1938 2,309,176 Dreyfus Jan. 26, 1943 2,741,532 Guthrie Apr. 10, 19562,873,269 Fasciati et al Feb. 10, 1959 2,892,828 Stephen June 30, 19592,895,785 Alsberg et al. July 21 1959 2,985,501 Gagarine May 23, 19613,009,920 Jaeger et al Nov. 21, 1961 FOREIGN PATENTS 149,986 AustriaJune 25, 1937 151,300 Austria Nov. 10, 1937 696,282 Great Britain Aug.26, 1953 OTHER REFERENCES Wegmann: Textil-Proxis, October 1958, p. 1056.

1. PROCESS FOR THE COLORATION OF CELLULOSE TEXTILE MATERIALS WITH AWATER-SOLUBLE DYESTUFF CHARACTERIZED BY ONE OF THE FORMULAE